Rubber compositions



but also otherwise disclose'd; a

'The complex organic materials are-phenolic compounds which are recovered from'certain pe- Patented July 3, 1945 I "PATE T: OFFICE i v V RUBBER COMPOSITIONS Per K. Frolich, .westfiield; N. :1; assignor, bymesne assignments, to J asco, Incorporated, a corpora,-

011:: Louisiana. No Drawing;

a u auano mbei- 18, 1939. Q Serial No. 299,964 y 4 Claims. 7 (01. 260 36) This invention'relates to improvements in the manufacture of rubber compositions and especially in the manufacture of rubber compositions that are soft and plastic enoughto be readily'incorporated with dry compounding ingredients.

Crude raw rubber is tough and non-plastic and before itwill absorb compounding ingredients it ismasticated on amill or in a mixer'until' it becomes plastic. 'Mastication of rubberis obtained by mechanically kneading, eitherby passing be-V tween rollers running atvariable speeds to subject the rubber to. compression followed by a shearing action, Orby mixing .in an enclosed mixer i to produce the same effect. Either of these methods requires a prolonged 'period of time and-another disadvantage is that great :heat' is thereby generated. 7 y

An object of this invention is to provide a complex organic material which when added to raw rubber will reduce the period of time required'for mastication to soften the rubber.

phenols may be further purifled by redistillation under vacuum. The boiling range of the phenols finally recovered I is generally higher than the.

boiling range of the petroleum fraction from which they'are'obtained." With suflicient treat? ment and redistillatio'n, the phenolic compounds can be substantially freed from hydrocarbons and other impuritiessuch as naphthem'cfaclds. U

The following example illustrates" the means used for obtaining these phenols? a Erample 1 'A sample of acid treated heating oil from East \TeXascrude was contacted in an agitatorwith .15

Another object of the invention is to'provide a complex 'organicmaterial that on being added to rubber will not only serve as a rubbersoftener, improve rubber as hereinafter material insoluble'in c'austic'whlch'settles outof the heating oiljwith the excess caustic and is then separated from the petroleum fraction. The intermediate layer formed in the above extraction and consisting of theccrud'e sodium phenate salts in alkaline solutlonis separated from the top'hea'tg ing oil layer and is washed with petroleum ether or naphtha to remove residual hydrocarbons, The solution of the salts is then treated with carbon dioxide or a weak mineral acid in suflicient'quancity to liberate only the phenols from the salts, any

, naphthenic acid salts being thus-kept undissociate d in'the solution. IThe liberated phenol s are 7 separated from the solution and may then be purified bydistillation, preferably under reduced pressure, or by blowing with air. Ii desired, thc

GravityAPI' 6.8 rColorK'Robinson) c Black Percent Water '20 Distillation--A. S. T. M..' C.

' Initial boiling point 98.9 a 5%0ff at: r 1', 102.2 10% off at 102.2 20% oil at e-1 1c0; 0 '30% off at 218.3 40% Off at 230.6 off at 238.9 Ofi at 250.0 offat 265.0 7

v off at j 284.4

oil at off at Cracked V The crudephenols were'then vacuumfdistilled;the' initial boiling point being about 30 C. at "5 mm 45c pressure. Various cuts were taken oil up to about -times"with"10% by volume of naphtha and then acidified with either carbondioxide or dilute acid for the precipitation of the phenols. Approx.-

imately 0.16% of crude phenols, based on the heating oil treated, was Obtained; Inspections of 2 these crude phenols'were as follows;

240' C. at 5 mmjpressur rpf the residue remaining in the stillwas a hard, tar-likesolid. jA sample of such phenols was fractionated and refractionated three times, the'following fractionsof the specified carbon hydrogen proportions being obtaincd in the last fractionation:

Boiling range. C at 2 mm. pressure Per cent (7.

p P raction if The petroleum phenols may be. characterized as containing a total of about 9 to 23 carbon atoms per molecule with about 3 to 1'7 of these carbon atoms present in saturated hydrocarbon groups, which show a hydrogendeficiency aslcomgpared to the hydrogen content of straight chain alkyl groups. This deficiency of hydrogen can be ascribed to the presence of cycle-aliphatic hydrocarbon'groups; Thus; while the saturated hydrocarbon substituent's' 'ot petroleumphenols' may 'be considered as mmmc, they do not have the paraflinicityof simple allryl group's. Moreover, I

be accounted by the phenolic group,"fa s can be seen from the'following analytical data':'

tained:

Fraction, Q BoilingrisngeflCl gm g? 79.09 mos V 79.35 v.16 78.19 8.82 80.66 8.54

Fraction 3 on further analysis was found to con- 'tainmore'oxygen as shown by the following analysis: v

Percentcarbon;,; 78.19 Percent hydrogen 80.82 Probable empirical formula g; Gulf-11501.5 Molecular weight (calm) 184 Molecular weight (found) 190.3

Sap. number of acetylated producticalc.) 340 Sap. number of acetylatedproduct.

analysis of fractions or these phenolic substances s'hows'that they contain more oxygen than could A'sample of petroleumjphenolfs'was"fractionated into four portionsand the following cuts ob-' (found) 256.67 'i It can be seen that if the oxygen atoms were phenolic, the acetylated product would have a saponiiication number of 340 mg. of'KOH/gm.

If only one of the oxygen atoms per molecule were phenolic the saponification number would be 246 which is in agreement with the value of 256 as found in the analysis. i

In the case of heavier distillates, such as lubrieating oil and heavier oils, the :use of aqueous be avoided -out the plasticizer. *These complex phenols 3 to 15% or more of the amount of solvent used. depending upon the concentration of the phenolic products and the type 01 stock being treated. About 1 to 10% by volume (on the oil treated) of the total solvent is generally used in the extraction. The preferred temperature is room temperature, although temperatures as low as 30 C. and up to 100 C. may be used. Countercurrent extraction is preferable.

The followingexample illustrates the extraction of phenols from heavydistillates:

Heavy Talang Akar kerosene (15 gallons).

' which has been previously treated with aqueous alkali and which boils substantially above 500 FQ. is'e'xtracted with one-half gallon of methyl alcohol containing one-half pound of potassium hydroxide'. "The mixture is centrifuged, the al coho'l layer'is distilled, and upon acidification of the, distillation residue 128 grams of crude pheno'l sear e recovered. These are vacuum distilled at -8 mm. presure.

The phenolic compounds so obtained are generally liquid mixtures varying in viscosity and boiling point, the values of these propertiesincreasing with increase in boiling point of the petroleum source of material. These phenols containfrom about carbon atoms per molecule to 27, carbon atoms or more.

In the higher boiling fractions, there is a deflciency; in; hydrogen-which indicates the presence of more than one nucleus or condensed nuclei.

Accordingto this invention. these complex petroleum phenols areused to soften rubber compositions; Whenrubber is treated with 2 to 10%,

preferably about 5%, of these petroleum phenols as such, reacted to form the corresponding tri- .aryl phosphates or in the form of theirmetal soaps, the following advantageous results are obtained. The treated rubber is more plastic at both both normal and elevated temperaturesand .a benzene solution containing-the added plasticizer has a marked decrease .in viscosit when compared with a similar solution of rubber with when used in rubber compositions possess also an age-resisting or oxidation-inhibiting property. To illustrate. as a specific example of another embodiment of this invention; a rubber composition wa made having the following formula:

7 Parts Smoked sheets 100 Stearic acid. I 1 Pztrafiine 1 Titanium dioxide Whiting Zinc oxide.- Sulfur 3 Captax) mercaptobenzothiazole 1.5

This base stock was divided into eight portions, one of which was used as a blank.' To the remaining' portions, 1% of each of the petroleum phenol cuts boiling between and 130 CI at 2 mm. pressure, 130 and C. at 2 mm, pres sure, and140 and 150 C. at-2 mm. pressure, re-

spectively, phenol bottoms, and of the commercial age-resistors; "Flectol H" (acetone-aniline reaction product), and'PAgerite resin D" (polymerized trimethyldihydroquirioline), and of simple phenols was added, respectively. These compositions were then mixed separately in a rubber mill and, after thorough mixing, were vulcanized in a mold at C. for 15 minutes to produce an optimum cure.

The iollowingtable presents the results obtained by the presence of a small amount of potroleum phenols in the rubber stocks as com-.

Accelerated aging. tests were carried out 'mosphere of oxygen ata pressure of pounds 7 per square inch.

tillation at 6 mm. of a sample of mixed phenols obtained in a manner similar to :that; described under Example '1) and'of the coal tar cresylic acids to separate portions'of a rubber base-:stock. Results were as follows? 1 1 i Base stock I Parts Smoked Sheets 100.0 Zinc oxide..-.... V5.0 Sulfur... -3.0 Stearic acid. 2. Di-o-tolyl guanidine 1. 0

Cure:-60 min. at 141- C.

v 1 v Composition aitei- H 1 Original composition 72 hrs. Bierer-Davis S 1 I Per cent bomb aging RP 6 Age resistor age'resis voi- Tensile Tensile strength, i g strength, cent I #lsqg in. e O #lsq. in. e

'Blank 3,150 7 100 o Petroleum phenols (B. P. 120l30 C. at 6 mm.) 2 3.1100 776 200 Petroleum phenols (B. P. 180-140 C. at 6 min.) 2 3,300 750 1,100 Petroleum phenols (B. P. ugh-15o C. at 6mm.):. 2 2,300 650 450 450 Barrettc high boiling cresylic' acids (B. P. 230?- 2 2,700 760 350 l (.orresponds roughly to 100-120 C. at 6 mm.

pared with those obtained by the presence of the commercially available products:

Effect of aging on tensile strengths of rubber compositions [Samples were aged for 96 hrs. in Biercr-Davis bomb] Tensile;1 'Iensiiila1 Pler cent strengt streng oss n 3 18mm before aging, after aging, tensile lbs./sq. in. lbs/sq. in. strength Blank .1 3. 050 2. 420 2Q. Flectol H" 2. 390 2,000 lo. Agci'ite resin D 2. 680 2. 180 18. Phenol cut #7.v 2, 450 2, 220 9. Phenol cut #8. 2. 635 2. 23g 15. Phenol cut #9 2, 445 1. 970 ii). Phenol bottoms. 2,610 1. 700 35.

The differences in the above stock after aging are very evident. Whereas the blank loses 20.5% of its tensile strength on aging, the same stock containing 1% of phenol cuts at l30 C. and 140 C. at 2 mm. pressure loses only 9.4% and 15.4% of its tensile strength respectively. These results are superior to those obtained with the commercially available products. Other proportions of the phenol cuts may be used from 6.1 to 10%.

The currently available age resisters cause discoloration of white or light-colored rubber when the rubber is exposed to sunlight or to a carbonarc Fadometer." The stockswhich were tested for age resistance were exposed with one-half of the sample washed to a Fadometer for 16 hours.

The following results were obtained:

, Appearance Sample (staining) Blank (base stock) None "Flectol H lgark. "Ageri't-e rosin D"..... \ei'y dark. Phenol cut. boiling range. 120-130 C. at 2 min. pressure cry light. Phenol cut, boiling range 130 F. at 2 mm. pressure Do, Phenol out, boiling range 140-150 0 at 2 mm pressure Li ht. Phenol bottoms Dark In another set of runs, cuts of petroleum phenols were compared with a sample of coal tar phenolic bodies boiling in approximately the same boiling range.- This was done by adding 2% of various phenol cuts (prepared by vacuum dis- It is apparent that the petroleum phenol cut, B. P. 130-140 C. at 6 mm., is quite effective as an age resistor, whereas the coal tar cresylic acid is not an age resistor.

The anti-oxidants of this invention appear to be uniquev in their ability not only to retard the loss in strength which accompanies aging but also to'suppress the flex cracking of rubber without 7 appreciably discoloring the rubber.

Although the anti-oxidants of this invention are useful in white or light-colored rubberbecause of their ability. to retard age deterioration without danger of undue discoloration, they may obviously be used also to retard the age deterioration of dark-colored rubber compositions or of compositions consisting of or containing unvulcanized rubber, gutta-percha, balata, synthetic rubber or synthetic rubberelike materials such' as polymers of butadiene', chloroprene, copolymers of diolefins and unsaturated nitriles which are formed bypolymerization at 30 to 100 C., and co-polymers obtainable from other polymerizable compounds, such as diolefins and styrene, vinyl naphthalene," etc.- Co-polyrners, which are obtained by reacting a low molecular weight olefin with a low molecular weight diolefin at relatively low temperatures, namely, below 0 C., and preferably below 50 C. to -80 C. and even as low as 103 C., in the presence of a suitable metallichalide catalyst such as aluminum chloride dissolved in methyl or ethyl chloride, may also be stabilized against age deterioration by this means whether or not they have been admixed with flllers, pigments, vulcanizing agents, and the like.

The anti-oxidants of this invention may likewise be employed not only by mechanical; incorporation into rubber but byapplication to its surface or'by mixing withliquid dispersions of rubber such'as latex and rubber cement, and may be employed either alone or together with other v 2. A composition of matter according to claim 1 in which the plastic-elastic substance is a synthetic rubbery high molecular weight conjugated diolefin polymer.

3. A composition of matter according to claim 1 inwhichthe high molecular weight conjugated diolefin'polymer is a polymer of butadiene.

4; A composition of matter according to claim 1 in which the plastic elastic substance is rubber. a PER K. FROLJCH. 

